U.S. patent application number 12/311034 was filed with the patent office on 2010-01-07 for polyolefin composition.
This patent application is currently assigned to MITSUI CHEMICALS, INC.. Invention is credited to Yuichi Ito, Masakazu Jitsukata, Hayato Kurita, Kazuki Mita, Ryoji Mori, Masahiko Okamoto, Toru Takehara.
Application Number | 20100004401 12/311034 |
Document ID | / |
Family ID | 39200411 |
Filed Date | 2010-01-07 |
United States Patent
Application |
20100004401 |
Kind Code |
A1 |
Ito; Yuichi ; et
al. |
January 7, 2010 |
Polyolefin composition
Abstract
[Problem] A polyolefin composition comprising an olefin-based
thermoplastic elastomer which is superior to conventional
olefin-based thermoplastic elastomers in scratch resistance and
abrasion resistance and has excellent heat aging resistance is
proposed. [Means for Solving the Problem] A polyolefin composition
comprising a syndiotactic .alpha.-olefin-based copolymer (A), a
polyolefin resin (B) (other than polybutene (C)), polybutene (C),
and if necessary, an ethylene-based copolymer rubber (D).
Inventors: |
Ito; Yuichi; (chiba-shi,
JP) ; Mita; Kazuki; (Chiba-shi, JP) ; Mori;
Ryoji; (Ichihara-shi, JP) ; Okamoto; Masahiko;
(Chiba-shi, JP) ; Takehara; Toru; (Ichihara-shi,
JP) ; Jitsukata; Masakazu; (Isumi-shi, JP) ;
Kurita; Hayato; (Nagoya-shi, JP) |
Correspondence
Address: |
FOLEY AND LARDNER LLP;SUITE 500
3000 K STREET NW
WASHINGTON
DC
20007
US
|
Assignee: |
MITSUI CHEMICALS, INC.
Ichihara-shi, Chiba
JP
|
Family ID: |
39200411 |
Appl. No.: |
12/311034 |
Filed: |
September 10, 2007 |
PCT Filed: |
September 10, 2007 |
PCT NO: |
PCT/JP2007/067608 |
371 Date: |
March 17, 2009 |
Current U.S.
Class: |
525/240 |
Current CPC
Class: |
C08L 23/10 20130101;
C08L 23/14 20130101; C08L 2207/12 20130101; C08L 2205/03 20130101;
C08L 23/06 20130101; C08L 23/0815 20130101; C08L 23/10 20130101;
C08L 23/14 20130101; C08L 23/16 20130101; C08L 23/20 20130101; C08L
2312/00 20130101; C08L 2666/02 20130101; C08L 2666/02 20130101 |
Class at
Publication: |
525/240 |
International
Class: |
C08L 23/20 20060101
C08L023/20 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 20, 2006 |
JP |
2006-254798 |
Claims
1. A polyolefin composition comprising: (A) a syndiotactic
.alpha.-olefin-based copolymer, (B) a polyolefin resin (other than
polybutene (C)), and (C) polybutene, wherein the syndiotactic
.alpha.-olefin-based copolymer (A) has properties that regarding
absorptions of methyl groups of propylene units in .sup.13C-NMR of
the copolymer (A) measured in a 1,2,4-trichlorobenzene solution,
the sum total of absorption intensities of peaks observed at 20.0
to 21.0 ppm on the basis of tetramethylsilane is not less than 0.5
of the absorption intensities at 19.0 to 22.0 ppm assigned to all
the methyl groups of propylene; the copolymer (A) comprises: (a-1)
repeating units derived from propylene, (a-2) repeating units
derived from ethylene, and if necessary, (a-3) repeating units
derived from an olefin of 4 to 20 carbon atoms, and/or (a-4)
repeating units derived from at least one polyene selected from
conjugated polyenes and non-conjugated polyenes; the copolymer (A)
contains the units (a-1) in amounts of 30 to 79% by mol, the units
(a-2) in amounts of 1 to 30% by mol, the units (a-3) in amounts of
0 to 50% by mol, (with the proviso that the units (a-2) and the
units (a-3) are contained in the total amount of 21 to 70% by mol
in 100% by mol of the total amount of the units (a-1), the units
(a-2) and the units (a-3)), and the units (a-4) in amounts of 0 to
30% by mol based on 100% by mol of the total amount of the units
(a-1), the units (a-2) and the units (a-3)); and the copolymer (A)
substantially has a syndiotactic structure.
2. The polyolefin composition as claimed in claim 1, wherein the
polyolefin resin (B) (other than polybutene (C)) is syndiotactic
and/or isotactic polypropylene.
3. The polyolefin composition as claimed in claim 1 or 2, wherein
the syndiotactic .alpha.-olefin-based copolymer (A) is blended in
an amount of 1 to 98 parts by weight, the polyolefin resin (B)
(other than polybutene (C)) is blended in an amount of 98 to 1 part
by weight, and the polybutene (C) is blended in an amount of 1 to
70 parts by weight, with the proviso that the total amount of the
components (A), (B) and (C) is 100 parts by weight.
4. The polyolefin composition as claimed in any one of claims 1 to
3, further comprising an ethylene-based copolymer rubber (D).
5. The polyolefin composition as claimed in claim 4, wherein the
ethylene-based copolymer rubber (D) is blended in an amount of 5 to
1000 parts by weight based on 100 parts by weight of the total
amount of the syndiotactic .alpha.-olefin-based copolymer (A), the
polyolefin resin (B) (other than polybutene (C)) and the polybutene
(C).
6. The polyolefin composition as claimed in claim 4 or 5, wherein
the ethylene-based copolymer rubber (D) has been crosslinked.
7. The polyolefin composition as claimed in any one of claims 1 to
6, wherein the syndiotactic .alpha.-olefin-based copolymer (A) does
not have a melting peak measured by a differential scanning
calorimeter (DSC) and has an intrinsic viscosity [72], as measured
in decalin at 135.degree. C., of 0.01 to 10 dl/g, a molecular
weight distribution (Mw/Mn), as determined by GPC, of not more than
4 and a glass transition temperature (Tg) of not higher than
-5.degree. C.
8. The polyolefin composition as claimed in any one of claims 1 to
7, wherein the syndiotactic .alpha.-olefin-based copolymer (A) has
been crosslinked.
9. The polyolefin composition as claimed in any one of claims 1 to
8, wherein the polybutene (C) is a homopolymer of 1-butene or a
copolymer consisting of 1-butene and an olefin other than 1-butene
and having a 1-butene content of not less than 50% by mol.
10. An automobile interior trim part produced from the polyolefin
composition of any one of claims 1 to 9.
11. The automobile interior trim part as claimed in claim 10, which
is produced by vacuum forming, stamping, powder slush molding or
injection molding.
12. An automobile seal part produced from the polyolefin
composition of any one of claims 1 to 9.
13. The automobile seal part as claimed in claim 12, which is
produced by extrusion molding or injection molding.
Description
TECHNICAL FIELD
[0001] The present invention relates to a polyolefin
composition.
BACKGROUND ART
[0002] For interior trim members of automobiles, a soft vinyl
chloride resin has been widely used in the past. Since the soft
vinyl chloride resin is excellent in molding processability into
parts and is relatively inexpensive, it has been used much for
interior trim skin materials of instrument panels, doors, ceilings
and the like, handle materials, lever knobs, various grips, etc. In
recent years, however, there has been pointed out a possibility
that the vinyl chloride resin becomes a cause of a poisonous gas
when incinerated, so that replacement of the soft vinyl chloride
resin used for the above parts with materials other than the soft
vinyl chloride resin has been studied.
[0003] Particularly for the automobile interior trim parts, an
olefin-based thermoplastic elastomer is most widely used as a
substitute for the soft vinyl chloride resin. The olefin-based
thermoplastic elastomer is a material excellent in various points
such that it is lightweight, is excellent in moldability and
processability into parts, can be readily recycled and generates no
poisonous gas during combustion, but on the other hand, it has a
disadvantage of poor scratch resistance.
[0004] On this account, the olefin-based thermoplastic elastomer
has not been used as it is for the parts requiring scratch
resistance, and in the actual circumstances, an elastomer having
been improved in scratch resistance by subjecting it to surface
treatment or the like is employed (see, for example, patent
document 1).
[0005] As the olefin-based thermoplastic elastomer having been
improved in scratch resistance, a composition obtained by adding a
hydrogenation product of a styrene/isoprene block copolymer having
a large quantity of 3,4-bonds of polyisoprene block moieties to a
crosslinked olefin-based thermoplastic elastomer containing
polypropylene and EPDM as basic components and prepared by dynamic
crosslinking has been proposed (see, for example, patent document
2). The hydrogenation product, however, not only has tackiness but
also is expensive as compared with the soft vinyl chloride resin
that has been mainly used in the past, and hence, use of the
composition is restricted in the actual circumstances.
[0006] Further, a composition having been improved in scratch
resistance by adding polybutene to the above-mentioned crosslinked
olefin-based thermoplastic elastomer has been proposed (see, for
example, patent document 3). This composition is superior to the
general-purpose crosslinked olefin-based thermoplastic elastomer in
scratch resistance, but actually, it is inferior in appearance to
the soft vinyl chloride resin that has been used in the past.
[0007] Under such circumstances as above, the present inventors
have found that compositions of a propylene/ethylene copolymer
having a syndiotactic structure, a propylene/butene/ethylene
copolymer having the same structure and a polyolefin resin are very
excellent in scratch resistance and abrasion resistance, and by
combining them with an appropriate lubricant, etc., they exhibit
scratch resistance and abrasion resistance comparable to those of
the soft vinyl chloride resin (see, for example, patent documents 4
and 5). These compositions, however, are inferior in heat aging
resistance, and the gloss varies in the aging test of 100.degree.
C. and about 24 hours, so that it is difficult to use them for
automobiles.
[0008] Patent document 1: Japanese Patent Publication No.
070742/1991
[0009] Patent document 2: Japanese Patent Laid-Open Publication No.
053789/1995
[0010] Patent document 3: Japanese Patent No. 2904708
[0011] Patent document 4: pamphlet of International Publication No.
2005/053951
[0012] Patent document 5: pamphlet of International Publication No.
2005/103141
DISCLOSURE OF THE INVENTION
Problem to be Solved by the Invention
[0013] The present invention is intended to solve the problems
associated with the prior art and proposes a polyolefin composition
which is superior to conventional polyolefin compositions in
scratch resistance and abrasion resistance and has excellent heat
aging resistance.
Means to Solve the Problem
Summary
[0014] The polyolefin-composition of the present invention is a
polyolefin composition comprising:
[0015] (A) a syndiotactic .alpha.-olefin-based copolymer,
[0016] (B) a polyolefin resin (other than polybutene (C)), and
[0017] (C) polybutene,
[0018] wherein the syndiotactic .alpha.-olefin-based copolymer (A)
has properties that regarding absorptions of methyl groups of
propylene units in .sup.13C-NMR of the copolymer (A) measured in a
1,2,4-trichlorobenzene solution, the sum total of absorption
intensities of peaks observed at 20.0 to 21.0 ppm on the basis of
tetramethylsilane is not less than 0.5 of the absorption
intensities at 19.0 to 22.0 ppm assigned to all the methyl groups
of propylene; the copolymer (A) comprises:
[0019] (a-1) repeating units derived from propylene,
[0020] (a-2) repeating units derived from ethylene,
[0021] and if necessary,
[0022] (a-3) repeating units derived from an olefin of 4 to 20
carbon atoms, and/or
[0023] (a-4) repeating units derived from at least one polyene
selected from conjugated polyenes and non-conjugated polyenes;
[0024] the copolymer (A) contains
[0025] the units (a-1) in amounts of 30 to 79% by mol,
[0026] the units (a-2) in amounts of 1 to 30% by mol,
[0027] the units (a-3) in amounts of 0 to 50% by mol,
[0028] (with the proviso that the units (a-2) and the units (a-3)
are contained in the total amount of 21 to 70% by mol in 100% by
mol of the total amount of the units, (a-1), the units (a-2) and
the units (a-3)), and
[0029] the units (a-4) in amounts of 0 to 30% by mol based on 100%
by mol of the total amount of the units (a-1), the units (a-2) and
the units (a-3)); and
[0030] the copolymer (A) substantially has a syndiotactic
structure.
[0031] The polyolefin resin (B) (other than polybutene (C)) is
preferably syndiotactic and/or isotactic polypropylene.
[0032] It is preferable that in the polyolefin composition, the
syndiotactic .alpha.-olefin-based copolymer (A) is blended in an
amount of 1 to 98 parts by weight, the polyolefin resin (B) (other
than polybutene (C)) is blended in an amount of 98 to 1 part by
weight, and the polybutene (C) is blended in an amount of 1 to 70
parts by weight, with the proviso that the total amount of the
components (A), (B) and (C) is 100 parts by weight.
[0033] The polyolefin composition may further comprise an
ethylene-based copolymer rubber (D), in addition to the
syndiotactic .alpha.-olefin-based copolymer (A), the polyolefin
resin (B) (other than polybutene (C)) and the polybutene (C), and
the ethylene-based copolymer rubber (D) may have been
crosslinked.
[0034] In the polyolefin composition, the ethylene-based copolymer
rubber (D) is preferably blended in an amount of 5 to 1000 parts by
weight based on 100 parts by weight of the total amount of the
syndiotactic .alpha.-olefin-based copolymer (A), the polyolefin
resin (B) (other than polybutene (C)) and the polybutene (C).
[0035] It is preferable that the syndiotactic .alpha.-olefin-based
copolymer (A) does not have a melting peak measured by a
differential scanning calorimeter (DSC) and has an intrinsic
viscosity [.eta.], as measured in decalin at 135.degree. C., of
0.01 to 10 dl/g, a molecular weight distribution (Mw/Mn), as
determined by GPC, of not more than 4 and a glass transition
temperature (Tg) of not higher than -5.degree. C.
[0036] The syndiotactic .alpha.-olefin-based copolymer (A) may have
been crosslinked.
[0037] The polybutene (C) is preferably a homopolymer of 1-butene
or a copolymer consisting of 1-butene and an olefin other than
1-butene and having a 1-butene content of not less than 50% by
mol.
[0038] The polyolefin composition is preferably used for an
automobile interior trim skin part produced by vacuum forming,
stamping, powder slush molding or injection molding, or an
automobile seal part produced by extrusion molding or injection
molding.
EFFECT OF THE INVENTION
[0039] Such a polyolefin composition as mentioned above is
excellent in moldability, heat resistance, scratch resistance,
abrasion resistance and flexibility balance and is also excellent
in heat aging resistance.
BRIEF DESCRIPTION OF THE DRAWING
[0040] FIG. 1 is an explanatory view showing a reciprocating
abrasion test method for grip.
DESCRIPTION OF NUMERICAL SYMBOLS
[0041] 1: grip [0042] 2: cotton canvas [0043] 3: weight of 300
g
BEST MODE FOR CARRYING OUT THE INVENTION
Detailed Description of the Invention
[0044] The polyolefin composition of the invention is described in
detail hereinafter.
[0045] The polyolefin composition of the invention is a polyolefin
composition comprising a syndiotactic .alpha.-olefin-based
copolymer (A), a polyolefin resin (B) (other than polybutene (C))
and polybutene (C).
[0046] In the composition, there are blended the syndiotactic
.alpha.-olefin-based copolymer (A) in an amount of 1 to 98 parts by
weight, preferably 10 to 95 parts by weight, more preferably 10 to
90 parts by weight, particularly preferably 20 to 90 parts by
weight, most preferably 30 to 85 parts by weight, the polyolefin
resin (B) (other than polybutene (C)) in an amount of 98 to 1 part
by weight, preferably 89 to 4 parts by weight, more preferably 77
to 7 parts by weight, particularly preferably 67 to 7 parts by
weight, most preferably 47 to 7 parts by weight, and the polybutene
(C) in an amount of 1 to 70 parts by weight, preferably 1 to 50
parts by weight, more preferably 3 to 30 parts by weight,
particularly preferably 3 to 25 parts by weight, most preferably 5
to 20 parts by weight, based on 100 parts by weight of the total
amount of the syndiotactic .alpha.-olefin-based copolymer (A), the
polyolefin resin (B) (other than polybutene (C)) and the polybutene
(C).
[0047] If necessary, an ethylene-based copolymer rubber (D) can be
further blended in an amount of 5 to 1000 parts by weight,
preferably 10 to 500 parts by weight, more preferably 15 to 300
parts by weight, particularly preferably 20 to 200 parts by weight,
most preferably 30 to 100 parts by weight, based on 100 parts by
weight of the total amount of the syndiotactic .alpha.-olefin-based
copolymer (A), the polyolefin resin (B) (other than polybutene (C))
and the polybutene (C).
[0048] Syndiotactic .alpha.-Olefin-Based Copolymer (A)
[0049] First, the syndiotactic .alpha.-olefin-based copolymer (A)
is described.
[0050] The syndiotactic .alpha.-olefin-based copolymer (A)
according to the invention is an .alpha.-olefin-based copolymer
substantially having a syndiotactic structure. The expression
"substantially having a syndiotactic structure" means that in
.sup.13C-NMR of the copolymer (A) measured in a
1,2,4-trichlorobenzene solution, the sum total of absorption
intensities of methyl groups of propylene units observed at about
20.0 to 21.0 ppm on the basis of tetramethylsilane is not less than
0.5, preferably not less than 0.6, more preferably not less than
0.7, of the sum total of absorption intensities at about 19.0 to
22.0 ppm assigned to propylene methyl.
[0051] The syndiotactic structure is measured in the following
manner. That is to say, 0.35 g of a sample is dissolved in 2.0 ml
of hexachlorobutadiene by heating. This solution is filtered
through a glass filter (G2), then 0.5 ml of deuterated benzene is
added, and the resulting solution is introduced into a NMR tube
having an inner diameter of 10 mm. Using a GX-500 type NMR
measuring device manufactured by JEOL Ltd., .sup.13C-NMR
measurement is carried out at 120.degree. C. The number of
integrating times is 10,000 or more. When the syndiotactic
.alpha.-olefin-based copolymer (A) is in such a range as above, the
copolymer (A) is excellent in syndiotactic properties and tends to
be excellent in transparency, flexibility and abrasion
resistance.
[0052] The syndiotactic .alpha.-olefin-based copolymer (A)
according to the invention contains propylene component units (a-1)
in amounts of 30 to 79% by mol, ethylene component units (a-2) in
amounts of 1 to 30% by mol and component units (a-3) derived from
an .alpha.-olefin of 4 to 20 carbon atoms in amounts of 0 to 50% by
mol (when the amount of all the component units in the copolymer
(A) is 100% by mol, the total amount of the ethylene component
units (a-2) and the component units (a-3) derived from an
.alpha.-olefin of 4 to 20 carbon atoms is in the range of 21 to 70%
by mol); the copolymer (A) preferably contains propylene component
units (a-1) in amounts of 35 to 75% by mol, ethylene component
units (a-2) in amounts of 3 to 25% by mol and component units (a-3)
derived from an .alpha.-olefin of 4 to 20 carbon atoms in amounts
of 10 to 45% by mol (when the amount of all the component units in
the copolymer (A) is 100% by mol, the total amount of the ethylene
component units (a-2) and the component units (a-3) derived from an
.alpha.-olefin of 4 to 20 carbon atoms is in the range of 25 to 65%
by mol); the copolymer (A) particularly preferably contains
propylene component units (a-1) in amounts of 35 to 65% by mol,
ethylene component units (a-2) in amounts of 3 to 25% by mol and
component units (a-3) derived from an .alpha.-olefin of 4 to 20
carbon atoms in amounts of 20 to 45% by mol (when the amount of all
the component units in the copolymer (A) is 100% by mol, the total
amount of the ethylene component units (a-2) and the component
units (a-3) derived from an .alpha.-olefin of 4 to 20 carbon atoms
is in the range of 35 to 65% by mol); and the copolymer (A) more
preferably contains propylene component units (a-1) in amounts of
40 to 65% by mol, ethylene component units (a-2) in amounts of 5 to
25% by mol and component units (a-3) derived from an .alpha.-olefin
of 4 to 20 carbon atoms in amounts of 20 to 40% by mol (when the
amount of all the component units in the copolymer (I) is 100% by
mol, the total amount of the ethylene component units (a-2) and the
component units (a-3) derived from an .alpha.-olefin of 4 to 20
carbon atoms is in the range of 35 to 60% by mol). The copolymer
(A) may further contain repeating units (a-4) derived from at least
one polyene selected from conjugated polyenes and non-conjugated
polyenes in amounts of 0 to 30% by mol, preferably 0 to 25% by mol,
based on 100% by mol of the total amount of the propylene component
units (a-1), the ethylene component units (a-2) and the component
units (a-3) derived from an .alpha.-olefin of 4 to 20 carbon atoms.
The syndiotactic .alpha.-olefin-based copolymer (A) containing the
propylene component (a-1), the ethylene component (a-2), the
component (a-3) derived from an .alpha.-olefin of 4 to 20 carbon
atoms, and the optionally used component (a-4) derived from at
least one polyene selected from conjugated polyenes and
non-conjugated polyenes in such amounts as above becomes excellent
in compatibility with the thermoplastic resin, and the resulting
polyolefin composition tends to exhibit flexibility, elastomeric
properties, scratch resistance and abrasion resistance.
[0053] The .alpha.-olefin used for preparing such a syndiotactic
.alpha.-olefin-based copolymer (A) is not specifically restricted
provided that the number of carbon atoms is in the range of 4 to
20, preferably 4 to 12, and the copolymer (A) may be straight-chain
or branched.
[0054] Examples of such .alpha.-olefins include 1-butene, 2-butene,
1-pentene, 1-hexene, 1-heptane, 1-octene, 1-nonene, 1-decene,
1-undecene, 1-dodecene, 3-methyl-1-butene, 3-methyl-1-pentene,
4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene,
4,4-dimethyl-1-pentene, 4-ethyl-1-hexene and 3-ethyl-1-hexene. Of
these, preferable are 1-butene, 1-hexene, 1-octene, 1-decene and
4-methyl-1-pentene, more preferable are 1-butene, 1-hexene,
1-octene and 1-decene, and particularly preferable is 1-butene.
[0055] These .alpha.-olefins can be used singly or in combination
of two or more kinds. For example, at least one .alpha.-olefin (a)
selected from .alpha.-olefins of 4 to 20 carbon atoms and an
.alpha.-olefin (b) which is selected from the .alpha.-olefins of 4
to 20 carbon atoms and is different from the .alpha.-olefin (a) can
be used in an (a)/(b) quantity ratio of (50 to 99% by mol)/(1 to
50% by mol) ((a)+(b)=100% by mol).
[0056] The repeating unit derived from at least one polyene
selected from conjugated polyenes and non-conjugated polyenes, said
polyene being used for preparing the syndiotactic
.alpha.-olefin-based copolymer (A), is a repeating unit derived
from at least one polyene selected from the following conjugated
polyenes and non-conjugated polyenes.
[0057] Examples of the conjugated polyenes include conjugated
dienes, such as 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene,
1,3-heptadiene, 1,3-octadiene, 1-phenyl-1,3-butadiene,
1-phenyl-2,4-pentadiene, isoprene, 2-ethyl-1,3-butadiene,
2-propyl-1,3-butadiene, 2-butyl-1,3-butadiene,
2-pentyl-1,3-butadiene, 2-hexyl-1,3-butadiene,
2-heptyl-1,3-butadiene, 2-octyl-1,3-butadiene and
2-phenyl-1,3-butadiene; and conjugated trienes, such as
1,3,5-hexatriene. Of these, butadiene, isoprene, pentadiene,
hexadiene and octadiene are preferable, and butadiene and isoprene
are particularly preferable from the viewpoint of excellent
copolymerizability.
[0058] Examples of the non-conjugated polyenes include:
[0059] non-conjugated dienes, such as dicyclopentadiene,
1,4-hexadiene, cyclooctadiene, methylenenorbornene,
ethylidenenorbornene, vinylnorbornene, 4-methyl-1,4-hexadiene,
5-methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene,
5-methyl-1,4-heptadiene, 5-ethyl-1,4-heptadiene,
5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene,
5-ethyl-1,5-heptadiene, 4-methyl-1,4-octadiene,
5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene,
5-ethyl-1,4-octadiene, 5-methyl-1,5-octadiene,
6-methyl-1,5-octadiene, 5-ethyl-1,5-octadiene,
6-ethyl-1,5-octadiene, 6-methyl-1,6-octadiene,
7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene,
4-methyl-1,4-nonadiene, 5-methyl-1,4-nonadiene,
4-ethyl-1,4-nonadiene, 5-ethyl-1,4-nonadiene,
5-methyl-1,5-nonadiene, 6-methyl-1,5-nonadiene,
5-ethyl-1,5-nonadiene, 6-ethyl-1,5-nonadiene,
6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene,
6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene,
7-methyl-1,7-nonadiene, 8-methyl-1,7-nonadiene,
7-ethyl-1,7-nonadiene, 5-methyl-1,4-decadiene,
5-ethyl-1,4-decadiene, 5-methyl-1,5-decadiene,
6-methyl-1,5-decadiene, 5-ethyl-1,5-decadiene,
6-ethyl-1,5-decadiene, 6-methyl-1,6-decadiene,
7-methyl-1,6-decadiene, 6-ethyl-1,6-decadiene,
7-ethyl-1,6-decadiene, 7-methyl-1,7-decadiene,
8-methyl-1,7-decadiene, 7-ethyl-1,7-decadiene,
8-ethyl-1,7-decadiene, 8-methyl-1,8-decadiene,
9-methyl-1,8-decadiene, 8-ethyl-1,8-decadiene and
9-methyl-1,8-undecadiene; and
[0060] non-conjugated trienes, such as
6,10-dimethyl-1,5,9-undecatriene, 4,8-dimethyl-1,4,8-decatriene,
5,9-dimethyl-1,4,8-decatriene, 6,9-dimethyl-1,5,8-decatriene,
6,8,9-trimethyl-1,5,8-decatriene,
6-ethyl-10-methyl-1,5,9-undecatriene, 4-ethylidene-1,6-octadiene,
7-methyl-4-ethylidene-1,6-octadiene,
4-ethylidene-8-methyl-1,7-nonadiene,
7-methyl-4-ethylidene-1,6-nonadiene,
7-ethyl-4-ethylidene-1,6-nonadiene,
6,7-dimethyl-4-ethylidene-1,6-octadiene,
6,7-dimethyl-4-ethylidene-1,6-nonadiene,
4-ethylidene-1,6-decadiene, 7-methyl-4-ethylidene-1,6-decadiene,
7-methyl-6-propyl-4-ethylidene-1,6-octadiene,
4-ethylidene-1,7-nonadiene, 8-methyl-4-ethylidene-1,7-nonadiene and
4-ethylidene-1,7-undecadiene.
[0061] Such non-conjugated polyenes are preferable from the
viewpoint that they are excellent in abrasion resistance when
crosslinked.
[0062] Of the above polyenes, 5-ethylidene-2-norbornene,
5-vinyl-2-norbornene, dicyclopentadiene (DCPD),
4,8-dimethyl-1,4,8-decatriene (DMDT) and
4-ethylidene-8-methyl-1,7-nonadiene (EMND) are desirable. Two or
more kinds of the units (a-4) may be contained.
[0063] In the syndiotactic .alpha.-olefin-based copolymer (A),
component units derived from an aromatic vinyl compound such as
styrene, component units derived from the above polyene-based
unsaturated compound (polyene) having two or more double bonds,
component units derived from alcohol, carboxylic acid, amine and
derivatives thereof, etc. may be contained.
[0064] The syndiotactic .alpha.-olefin-based copolymer (A)
desirably has an intrinsic viscosity [.eta.], as measured in
decalin at 135.degree. C., of usually 0.01 to 10 dl/g, preferably
0.05 to 10 dl/g. When the intrinsic viscosity [.eta.] of the
syndiotactic .alpha.-olefin-based copolymer (A) is in the above
range, the syndiotactic .alpha.-olefin-based copolymer (A) is
excellent in properties, such as weathering resistance, ozone
resistance, heat aging resistance, low-temperature properties and
dynamic fatigue resistance.
[0065] The syndiotactic .alpha.-olefin-based copolymer (A) has a
single glass transition temperature, and the glass transition
temperature Tg as measured by a differential scanning calorimeter
(DSC) is desired to be usually not higher than -5.degree. C.,
preferably not higher than -10.degree. C., particularly preferably
not higher than -15.degree. C. When the glass transition
temperature Tg of the syndiotactic .alpha.-olefin-based copolymer
(A) is in the above range, the copolymer (A) is excellent in
low-temperature resistance and low-temperature properties.
[0066] The syndiotactic .alpha.-olefin-based copolymer (A) has a
molecular weight distribution (Mw/Mn, in terms of polystyrene, Mw:
weight-average molecular weight, Mn: number-average molecular
weight), as measured by GPC, of not higher than 4.0, preferably 1.5
to 3.0. When the molecular weight distribution is in this range,
the polyolefin composition becomes excellent in scratch resistance,
abrasion resistance and impact resistance, so that such a molecular
weight distribution is preferable. Further, it is desirable that a
melting peak measured by a differential scanning calorimeter (DSC)
is not present. In this case, the polyolefin composition becomes
excellent in flexibility, scratch resistance, abrasion resistance
and impact resistance
[0067] Preparation of Syndiotactic .alpha.-Olefin-Based Copolymer
(A)
[0068] Such a syndiotactic structure .alpha.-olefin-based copolymer
(A) can be obtained by copolymerizing propylene, ethylene and an
.alpha.-olefin in the presence of a metallocene catalyst described
below.
[0069] As such a metallocene catalyst, there can be mentioned at
least one catalyst system comprising:
[0070] (x) a transition metal compound represented by the following
formula (1), and
[0071] (y) at least one compound selected from [0072] (y-1) a
compound which reacts with a transition metal M in the above
transition metal compound (a) to form an ionic complex, [0073]
(y-2) an organoaluminum oxy-compound, and [0074] (y-3) an
organoaluminum compound.
##STR00001##
[0075] In the formula (1), M is Ti, Zr, Hf, Rn, Nd, Sm or R,
Cp.sup.1 and Cp.sup.2 are each a cyclopentadienyl group, an indenyl
group, a fluorenyl group or a derivative group thereof, said group
being .pi.-bonded to M, X.sup.1 and X.sup.2 are each an anionic
ligand or a neutral Lewis base ligand, and Z is an atom of C, O, B,
S, Ge, Si or Sn, or a group containing any of these atoms.
[0076] Of such transition metal compounds represented by the
formula (1), preferable are transition metal compounds wherein
Cp.sup.1 and Cp.sup.2 are groups different from each other, and
more preferable are transition metal compounds wherein any one
group of Cp.sup.1 and Cp.sup.2 is a cyclopentadienyl group or its
derivative group and the other group is a fluorenyl group or its
derivative group. Of these, transition metal compounds wherein any
one group of Cp1 and Cp2 is a cyclopentadienyl group or its
derivative group and the other group is a fluorenyl group or its
derivative group are preferable.
[0077] In the present invention, such a metallocene catalyst as
above is preferably used as a catalyst for preparing the
syndiotactic .alpha.-olefin copolymer (A), but according to
circumstances, a titanium catalyst comprising a solid titanium
catalyst component and an organoaluminum compound or a vanadium
catalyst comprising a soluble vanadium compound and an
organoaluminum compound, said titanium or vanadium catalyst being a
catalyst other than the above metallocene catalyst and hitherto
publicly known, is also employable.
[0078] In the present invention, ethylene, propylene, and if
necessary, an olefin and/or at least one polyene selected from
conjugated polyenes and non-conjugated polyenes are copolymerized
in the presence of such a metallocene catalyst as above usually in
a liquid phase. In this case, a hydrocarbon solvent is generally
used, but propylene may be used as a solvent. Copolymerization can
be carried out by any of a batch process and a continuous
process.
[0079] When the copolymerization is carried out by a batch process
using the metallocene catalyst, the transition metal compound (x)
is used in the polymerization system in an amount of usually
0.00005 to 1 mmol, preferably 0.0001 to 0.5 mmol, based on 1 liter
of the polymerization volume.
[0080] The ionizing ionic compound (y-1) is used in such an amount
that the molar ratio ((y-1)/(x)) of the ionizing ionic compound
(y-1) to the transition metal compound (x) becomes 0.5 to 20,
preferably 1 to 10.
[0081] The organoaluminum oxy-compound (y-2) is used in such an
amount that the molar ratio (Al/M) of aluminum atom (Al) in the
organoaluminum oxy-compound (y-2) to the transition metal atom (M)
in the transition metal compound (x) becomes 1 to 10000, preferably
10 to 5000. The organoaluminum compound (y-3) is used in an amount
of usually about 0 to 5 mmol, preferably about 0 to 2 mmol, based
on 1 liter to the polymerization volume.
[0082] The copolymerization reaction is carried out under the
conditions of a temperature of usually -20 to 150.degree. C.,
preferably 0 to 120.degree. C., more preferably 0 to 100.degree.
C., and a pressure of more than 0 but not more than 80 kg/cm.sup.2,
preferably more than 0 but not more than 50 kg/cm.sup.2.
[0083] Although the reaction time (average residence time in the
case where polymerization is carried out by a continuous process)
varies depending upon the conditions such as catalyst concentration
and polymerization temperature, it is in the range of usually 5
minutes to 3 hours, preferably 10 minutes to 1.5 hours.
[0084] Ethylene, propylene and an olefin are each fed to the
polymerization system in such an amount that a syndiotactic
.alpha.-olefin copolymer (A) having the aforesaid specific
composition is obtained. In the copolymerization, a, molecular
weight modifier such as hydrogen may be used. When ethylene,
propylene and an .alpha.-olefin are copolymerized as above, the
syndiotactic .alpha.-olefin copolymer (A) is obtained usually as a
polymerization liquid containing it. This polymerization liquid is
processed in a conventional way, whereby the syndiotactic
.alpha.-olefin copolymer (A) is obtained.
[0085] Polyolefin Resin (B) (Other than Polybutene (C))
[0086] The polyolefin resin for use in the invention is an olefin
polymer having crystallizability, and examples of suitable raw
material olefins include ethylene, propylene, 1-butene, 1-pentene,
1-hexene, 1-octene, 1-decene, 2-methyl-1-propene,
3-methyl-1-pentene, 4-methyl-1-pentene and 5-methyl-1-hexene. These
olefins are used singly or as a mixture of two or more kinds.
Examples of such polyolefins include olefin homopolymers, such as
polyethylene, polypropylene, polymethylpentene and
polymethylbutene, and olefin copolymers, such as a
propylene/ethylene random copolymer, but the polybutene (C) is not
included. Of these, polypropylene, a propylene/ethylene random
copolymer and a propylene/ethylene block copolymer are preferable,
and in particular, polypropylene having a melt flow rate, as
measured at 230.degree. C. under a load of 2.16 kg, of 0.1 to 200
g/10 min is most preferable. The content of repeating units derived
from propylene is preferably not less than 80% by mol. From the
viewpoint of heat resistance, a polyolefin resin having a
crystallinity, as determined by wide-angle X-ray diffractometry or
the like, of not less than 5%, preferably not less than 20%, more
preferably not less than 40%, is used.
[0087] As the polypropylene, any of isotactic polypropylene and
syndiotactic polypropylene may be used.
[0088] Such thermoplastic resins as above may be used singly or may
be used in combination of two or more kinds. Together with the
above thermoplastic resins, other thermoplastic resins may be
used.
[0089] Polybutene (C)
[0090] The polybutene (C) for use in the invention is a homopolymer
of 1-butene or a copolymer of 1-butene and an olefin other than
1-butene. Examples of the olefins include ethylene, propylene,
1-pentene, 1-hexene, 1-octene, 1-decene, 2-methyl-1-propene,
3-methyl-1-pentene, 4-methyl-1-pentene and 5-methyl-1-hexcene.
These olefins are used singly or as a mixture of two or more kinds.
Examples of such polyolefins include 1-butene/ethylene random
copolymer, 1-butene/propylene random copolymer,
1-butene/methylpentene copolymer, 1-butene/methylbutene copolymer
and 1-butene/propylene/ethylene copolymer. In such a copolymer, the
1-butene content is preferably not less than 50% by mol from the
viewpoint of heat aging resistance. The polybutene (C) is
preferably isotactic polybutene.
[0091] Ethylene-Based Copolymer Rubber (D)
[0092] The ethylene-based copolymer rubber (D) for use in the
invention is an amorphous random elastomeric copolymer rubber
consisting of ethylene and an .alpha.-olefin of 3 to 20 carbon
atoms or an amorphous random elastomeric copolymer rubber
consisting of ethylene, an .alpha.-olefin of 3 to 20 carbon atoms
and a non-conjugated polyene.
[0093] In the ethylene-based copolymer (D), the molar ratio of
ethylene to the .alpha.-olefin is in the range of usually 40/60 to
85/15, preferably 60/40 to 83/17.
[0094] Examples of the non-conjugated polyenes include
dicyclopentadiene, 1,4-hexadiene, cyclooctadiene,
methylenenorbornene, ethylidenenorbornene and vinylnorbornene. Of
these, ethylene/propylene/non-conjugated diene copolymer rubbers
and ethylene/1-butene/non-conjugated diene copolymer rubbers are
preferable. In particular, ethylene/propylene/non-conjugated diene
copolymer rubbers are preferable, and of these, an
ethylene/propylene/ethylidenenorbornene copolymer rubber and an
ethylene/propylene/vinylnorbornene copolymer rubber are
particularly preferable.
[0095] The Mooney viscosity [ML1+4 (100.degree. C.)] of the
ethylene-based copolymer rubber (D) for use in the invention is
desired to be in the range of 50 to 300, preferably 100 to 200.
[0096] The iodine value of the ethylene-based copolymer rubber (D)
is in the range of preferably 3 to 30, particularly preferably 5 to
25.
[0097] The ethylene-based copolymer rubber (D) for use in the
invention may be an oil-extended product containing a softener. As
the softener employable in the oil-extended product, a softener
usually used for rubbers can be employed.
[0098] Examples of the softeners include:
[0099] petroleum-based substances, such as process oil, lubricating
oil, paraffin, liquid paraffin, petroleum asphalt and vaseline;
[0100] synthetic oils, such as low- or medium-molecular weight
ethylene/.alpha.-olefin random copolymer;
[0101] coal tars, such as coal tar and coal tar pitch;
[0102] fatty oils, such as castor oil, linseed oil, rapeseed oil,
soybean oil and coconut oil;
[0103] waxes, such as tall oil, beeswax, carnauba wax and
lanolin;
[0104] fatty acids or metallic salts thereof, such as ricinolic
acid, palmitic acid, stearic acid, barium stearate and calcium
stearate;
[0105] synthetic high-molecular weight substances, such as
petroleum resin, coumarone-indene resin and atactic
polypropylene;
[0106] ester type plasticizers, such as dioctyl phthalate, dioctyl
adipate and dioctyl sebacate; and
[0107] others, such as microcrystalline wax, factice, liquid
polybutadiene, modified liquid polybutadiene and liquid
Thiokol.
[0108] Of these softeners, paraffinic process oil or low-molecular
weight ethylene/.alpha.-olefin random copolymer is particularly
preferable, and further, paraffinic process oil of high viscosity
type having a low content of a low-molecular weight component that
is easily evaporated is particularly preferable. The "high
viscosity type" used herein means an oil having a dynamic viscosity
at 40.degree. C. of 100 to 10000 centistokes.
[0109] In the present invention, the softener is used in an amount
of not more than 150 parts by weight, preferably 2 to 100 parts by
weight, more preferably 5 to 60 parts by weight, based on 100 parts
by weight of the ethylene-based copolymer rubber (D).
[0110] Other Components
[0111] In addition to the syndiotactic .alpha.-olefin-based
copolymer (A), the polyolefin resin (B), the polybutene (C) and the
ethylene-based copolymer rubber (D), other thermoplastic resins can
be added in the invention within limits not detrimental to the
merits of the polyolefin composition of the invention. As the other
thermoplastic resins, thermoplastic resins having a melting point
of not lower than 50.degree. C., preferably not lower than
80.degree. C., can be used without any restriction, and when a
clear melting point is not present, thermoplastic resins having a
glass transition temperature of not lower than 40.degree. C.,
preferably not lower than 80.degree. C., can be used without any
restriction. Examples of such thermoplastic resins include
crystalline thermoplastic resins, such as polyamide, polyester,
polyacetal, soft polyvinyl chloride, polyamide elastomer, polester
elastomer and polyurethane elastomer, and non-crystalline
thermoplastic resins, such as polystyrene,
acrylonitrile/butadiene/styrene copolymer (ABS), polycarbonate and
polyphenylene oxide.
[0112] In the present invention, not only the ethylene-based
copolymer rubber (D) but also a combination of the ethylene-based
copolymer rubber (D) and a rubber other than the ethylene-based
copolymer rubber (D) can be used within limits not detrimental to
the object of the present invention. Examples of such rubbers other
than the ethylene-based copolymer rubber (D) include
propylene/ethylene copolymer rubber (propylene content: not less
than 60% by mol), propylene/.alpha.-olefin copolymer rubber,
styrene/butadiene rubber and its hydrogenation product,
styrene/isoprene rubber and its hydrogenation product,
polybutadiene rubber, polyisoprene rubber, nitrile rubber, butyl
rubber, polyisobutylene rubber, natural rubber and silicone
rubber.
[0113] In the polyolefin composition of the invention, a softener
and/or an inorganic filler may be blended in addition to the
syndiotactic .alpha.-olefin-based copolymer (A), the polyolefin
resin (B) (other than polybutene (C)), the polybutene (C) and the
ethylene-based copolymer rubber (D).
[0114] The softener may be used for oil-extending the
ethylene-based copolymer rubber (D), as previously described, or
may be added later without oil-extending the ethylene-based
copolymer rubber (D). Also in the case where the softener is added
later without oil-extending the ethylene-based copolymer rubber
(D), the same softener as previously described can be employed.
[0115] In the case where the softener is added later without
oil-extending the ethylene-based copolymer rubber (D), the amount
of the softener including the oil-extending portion is not more
than 100 parts by weight, preferably 3 to 80 parts by weight, more
preferably 5 to 50 parts by weight, based on 100 parts by weight of
the total amount of the syndiotactic .alpha.-olefin-based copolymer
(A), the polyolefin resin (B) (other than polybutene (C)), the
polybutene (C) and the ethylene-based copolymer rubber (D) that is
used when needed. When the softener is used in the above amount,
the resulting composition is excellent in flowability in the
molding process, and mechanical properties of a molded product of
the composition are not lowered. If the amount of the softener used
in the invention exceeds 100 parts by weight, heat resistance of
the resulting composition tends to be lowered.
[0116] Examples of the inorganic fillers employable in the
invention include calcium carbonate, calcium silicate, clay,
kaolin, talc, silica, diatomaceous earth, mica powder, asbestos,
alumina, barium sulfate, aluminum sulfate, calcium sulfate, basic
magnesium carbonate, molybdenum disulfide, graphite, glass fiber,
glass bulb, Shirasu balloon, basic magnesium sulfate whisker,
calcium titanate whisker and aluminum borate whisker.
[0117] In the present invention, the inorganic filler is used in an
amount of not more than 100 parts by weight, preferably 2 to 30
parts by weight, based on 100 parts by weight of the total amount
of the syndiotactic .alpha.-olefin-based copolymer (A), the
polyolefin resin (B) (other than polybutene (C)), the polybutene
(C) and the ethylene-based copolymer rubber (D) that is used when
needed. If the amount of the inorganic filler used in the invention
exceeds 100 parts by weight, elastomeric properties and molding
processability of the resulting composition tend to be lowered.
[0118] To the polyolefin composition of the invention can be
further added additives hitherto publicly known, such as heat
stabilizer, anti-aging agent, weathering stabilizer, antistatic
agent, crystal nucleating agent and lubricant, within limits not
detrimental to the object of the present invention. In particular,
the lubricant contributes to further enhancing scratch resistance
and abrasion resistance of the resulting polyolefin composition,
and examples of the lubricants include higher fatty acid amide,
metallic soap, wax, silicone oil and fluorine-based polymer. Above
all, higher fatty acid amide, silicone oil or fluorine-based
polymer is used in the polyolefin composition of the invention.
Examples of the higher fatty acid amides include saturated fatty
acid amides, such as lauric acid amide, palmitic acid amide,
stearic acid amide and behenic acid amide; unsaturated fatty acid
amides, such as erucic acid amide, oleic acid amide, brassidic acid
amide and elaidic acid amide; and bisfatty acid amides, such as
methylenebisstearic acid amide, methylenebisoleic acid amide,
ethylenebisstearic acid amide and ethylenebisoleic acid amide.
Examples of the silicone oils include dimethyl silicone oil,
phenylmethyl silicone oil, alkyl silicone oil, fluorosilicone oil,
tetramethyl tetraphenyl trisiloxane and modified silicone oil.
Specifically, polytetrafluoroethylene, vinylidene fluoride
copolymer, etc. can be mentioned. Of these, preferable are erucic
acid amide, oleic acid amide, ethylenebisoleic acid amide, dimethyl
silicone oil, phenylmethyl silicone oil, alkyl silicone oil,
polytetrafluoroethylene and vinylidene fluoride copolymer, and
particularly preferable are erucic acid amide, oleic acid amide,
dimethyl silicone oil and vinylidene fluoride copolymer.
[0119] Polyolefin Composition
[0120] The polyolefin composition of the invention is obtained by
mixing the syndiotactic .alpha.-olefin-based copolymer (A), the
polyolefin resin (B) (other than polybutene (C)), the polybutene
(C), the ethylene-based copolymer rubber (D) that is used when
needed, and the softener and/or the inorganic filler that is
blended when needed, and/or the additives, then dynamically
heat-treating the mixture to obtain a composition and molding the
composition into a desired shape. The expression "dynamically
heat-treating" used herein means that the mixture is kneaded in a
molten state.
[0121] All the components may be dynamically heat-treated at once;
or it is also possible that two or more of the syndiotactic
.alpha.-olefin-based copolymer (A), the polyolefin resin (B) (other
than polybutene (C)), the polybutene (C) and the ethylene-based
copolymer rubber (D) that is used when needed are dynamically
heat-treated in advance together with the softener and/or the
inorganic filler that is blended when needed, and/or the additives,
then one or more of the syndiotactic .alpha.-olefin-based copolymer
(A), the polyolefin resin (B) (other than polybutene (C)), the
polybutene (C) and the ethylene-based copolymer rubber (D) that is
used when needed, and the softener and/or the inorganic filler that
is blended when needed, and/or the additives are added, and they
are dynamically heat-treated again.
[0122] In the case where the dynamic heat treatment is carried out
in the presence of a crosslinking agent, the ethylene-based
copolymer rubber (D) can be crosslinked. By crosslinking the
ethylene-based copolymer rubber (D), heat resistance of the
interior trim skin according to the invention is improved. By
carrying out the dynamic heat treatment in the presence of a
crosslinking agent, the syndiotactic .alpha.-olefin-based copolymer
(A) can be also crosslinked. By crosslinking the syndiotactic
.alpha.-olefin-based copolymer (A), heat resistance of the interior
trim skin according to the invention is improved. In particular,
because the syndiotactic .alpha.-olefin-based copolymer (A)
contains the units (a-4), crosslinking efficiency is enhanced, and
this contributes to enhancement of heat resistance and elastomeric
properties.
[0123] Examples of the crosslinking agents used in the above case
include crosslinking agents generally used for thermosetting type
rubbers, such as organic peroxide, phenolic resin, sulfur,
hydrosilicone compound, amino resin, quinone or its derivative,
amine compound, azo compound, epoxy compound and isocyanate. Of
these crosslinking agents, organic peroxide is particularly
preferable.
[0124] Examples of the organic peroxides for use in the invention
include dicumyl peroxide, di-tert-butyl peroxide,
2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane,
2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyne-3,1,3-bis(tert-butylperoxyis-
opropyl)benzene,
1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane,
n-butyl-4,4-bis(tert-butylperoxy)valerate, benzoyl peroxide,
p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl
peroxybenzoate, tert-butyl perbenzoate, tert-butylperoxyisopropyl
carbonate, diacetyl peroxide, lauroyl peroxide and tert-butylcumyl
peroxide.
[0125] Of these, bifunctional organic peroxides, such as
2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane,
2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyne-3 and
1,3-bis(tert-butylperoxyisopropyl)benzene, are particularly
preferable from the viewpoints of reactivity, odor and scorch
stability. Of these, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane
is most preferable.
[0126] Such an organic peroxide is used in an amount of 0.02 to 3
parts by weight, preferably 0.05 to 1 part by weight, based on 100
parts by weight of the whole substance to be treated.
[0127] In the crosslinking treatment with the organic peroxide in
the invention, a peroxy crosslinking assistant, such as sulfur,
p-quinonedioxime, p,p'-dibenzoyl quinonedioxime,
N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine or
trimethylolpropane-N,N'-m-phenylenedimaleimide, or a polyfunctional
methacrylate monomer, such as divinylbenzene, triallyl cyanurate,
ethylene glycol dimethacrylate, diethylene glycol dimethacrylate,
polyethylene glycol dimethacrylate, trimethylolpropane
trimethacrylate or allyl methacrylate, or a polyfunctional vinyl
monomer, such as vinyl butyrate or vinyl stearate, can be
blended.
[0128] By the use of such a compound as above, uniform and mild
crosslinking reaction can be expected. In particular,
divinylbenzene is most preferable in the invention. Divinylbenzene
is easy to handle, and it has excellent compatibility with the
syndiotactic .alpha.-olefin-based copolymer (A) that is a main
component of the above substance to be crosslinked, the polyolefin
resin (B) (other than polybutene (C)) and the ethylene-based
copolymer rubber (D). Moreover, divinylbenzene has a function of
solubilizing the organic peroxide and serves as a dispersant for
the organic peroxide. Hence, the crosslinking effect due to heat
treatment is homogeneous, and a composition having a good balance
between flowability and other properties is obtained.
[0129] The compound, such as the above crosslinking assistant or
polyfunctional vinyl monomer, is used in an amount of usually not
more than 5 parts by weight, preferably 0 to 3 parts by weight,
more preferably 0.2 to 3 parts by weight, particularly preferably
0.3 to 3 parts by weight, based on 100 parts by weight of the
substance to be treated.
[0130] In order to accelerate decomposition of the organic
peroxide, a decomposition accelerator, e.g., tertiary amine, such
as triethylamine, tributylamine or 2,4,6-tri(dimethylamino)phenol,
or naphthenic acid salt of aluminum, cobalt, vanadium, copper,
calcium, zirconium, manganese, magnesium, lead, mercury or the
like, may be used.
[0131] The dynamic heat treatment in the invention is preferably
carried out in a non-open type apparatus and is preferably carried
out in an atmosphere of an inert gas such as nitrogen or carbonic
acid gas. The temperature of the heat treatment is in the range of
a melting point of the polyolefin resin (B) to 300.degree. C. and
is in the range of usually 150 to 290.degree. C., preferably 170 to
270.degree. C. The kneading time is in the range of usually 1 to 20
minutes, preferably 1 to 10 minutes. The shear force applied is in
the range of 10 to 10,000 sec.sup.-1, preferably 100 to 5,000
sec.sup.-1, in terms of shear rate.
[0132] Although a mixing roll, an intensive mixer (e.g., Banbury
mixer, kneader), a single-screw or twin-screw extruder or the like
can be used as the kneading apparatus, a non-open type apparatus is
preferable.
[0133] After the above dynamic heat treatment, the composition is
desired to be statically heat-treated with hot air. The heat
treatment is preferably carried out at 80 to 130.degree. C. for
about 1 to 10 hours. By this heat treatment, residues of the
crosslinking agent, etc. can be removed, and odor of the resulting
article can be reduced, or an article excellent in fogging
properties can be obtained.
[0134] Preferred uses of the polyolefin composition of the
invention are specifically as follows.
[0135] Automobile Interior Trim Parts
[0136] (i) Instrument panel skin, door skin, ceiling skin, console
skin, etc. obtained by vacuum forming or stamping of a sheet molded
product that is obtained by extrusion molding or calendering the
composition of the invention.
[0137] (ii) Instrument panel skin, door skin, ceiling skin, ceiling
skin and console skin, etc. obtained by pulverizing the composition
of the invention into a powder having a particle diameter of not
more than 1.0 mm and subjecting the powder to powder slush
molding.
[0138] (iii) Various skins obtained by injection molding of the
composition of the invention, such as handle skin, console skin,
armrest skin, shift knob skin, parking lever grip skin, assist grip
skin and seat adjustment grip skin. In this case, a substrate of an
olefin-based resin and the skin of the invention can be integrally
produced by successive injection molding or simultaneous injection
molding of the composition and the olefin-based resin such as
polypropylene.
[0139] Automobile Seal Parts
[0140] Examples of the automobile seal parts according to the
invention include the following ones.
[0141] (i) Side molding, bumper molding, roof molding, window
molding, glass run channel, weatherstrip molding, belt molding,
etc. obtained by single layer extrusion molding.
[0142] (ii) Side molding, bumper molding, roof molding, window
molding, glass run channel, weatherstrip molding, belt molding,
etc. obtained by multilayer lamination extrusion molding of the
composition and other materials. In this case, the composition of
the invention is used for parts requiring at least scratch
resistance and abrasion resistance.
[0143] (iii) Main bodies, end parts and corner parts of side
molding, bumper molding, roof molding, window molding, glass run
channel, weatherstrip molding, belt molding, etc., which are
obtained by injection molding.
EXAMPLES
Polymerization Example 1
Preparation of Syndiotactic Propylene/Butene/Ethylene Random
Copolymer (A-1)
[0144] In a 2000 ml polymerization apparatus thoroughly purged with
nitrogen, 100 ml of dry hexane, 480 g of 1-butene and
triisobutylaluminum (1.0 mmol) were placed at ordinary temperature.
Then, the internal temperature of the polymerization apparatus was
raised to 35.degree. C., and the polymerization apparatus was
pressurized to 0.54 MPa with propylene and then pressurized to 0.62
MPa with ethylene. Thereafter, a toluene solution in which 0.005
mmol of diphenylmethylene(cyclopentadienyl)fluorenyl zirconium
dichloride and 1.5 mmol (in terms of aluminum) of methylaluminoxane
(available from Tosoh Finechem Corporation) had been contacted was
introduced into the polymerizer. With maintaining the internal
temperature at 35.degree. C. and the ethylene pressure at 0.62 MPa,
polymerization was carried out for 5 minutes, and 20 ml of methanol
was added to terminate polymerization. After the pressure was
released, a polymer was precipitated from the polymer solution in 2
liters of methanol, and the polymer was dried under vacuum at
130.degree. C. for 12 hours. The amount of the polymer obtained was
36.1 g. The polymer had composition of a propylene content of 61.3%
by mol, an ethylene content of 10.3% by mol and a 1-butene content
of 28.4% by mol, and the polymer had an intrinsic viscosity [.eta.]
of 2.67 dl/g and a glass transition temperature Tg of -27.7.degree.
C. Further, any melting peak was not present, and the molecular
weight distribution as determined by GPC was 2.0. As for the
absorptions of methyl groups of propylene units in .sup.13C-NMR of
the polymer measured in a 1,2,4-trichlorobenzene solution, the sum
total of absorption intensities observed at about 20.0 to 21.0 ppm
on the basis of tetramethylsilane was 0.8 of the absorption
intensities at about 19.0 to 22.0 ppm assigned to propylene
methyl.
Polymerization Example 2
Preparation of Syndiotactic Propylene/Ethylene Random Copolymer
(A-2)
[0145] In a 1.5-liter autoclave vacuum dried and purged with
nitrogen, 750 ml of heptane was placed at ordinary temperature,
then 0.3 ml of a toluene solution (1.0 mmol/ml) of
triisobutylaluminum was added so that its amount would become 0.3
mmol in terms of aluminum atom, and 50.7 liters of propylene were
introduced (25.degree. C., 1 atm) with stirring. Then, temperature
rise was started, and a temperature of 30.degree. C. was reached.
Thereafter, the system was pressurized to 5.5 kg/cm.sup.2G with
ethylene, and 3.75 ml of a heptane solution (0.0002 mmol/ml) of
diphenylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride
synthesized by a publicly known process and 2.0 ml of a toluene
solution (0.002 mmol/ml) of triphenylcarbenium
tetra(pentafluorenyl)borate were added to initiate copolymerization
of propylene and ethylene. As for the catalyst concentration at
this time, the
diphenylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride
concentration in the whole system was 0.001 mmol/liter, and the
triphenylcarbenium tetra(pentafluorenyl)borate concentration in the
whole system was 0.004 mmol/liter.
[0146] During the polymerization, ethylene was continuously fed to
maintain the internal pressure at 5.5 kg/cm.sup.2G. After 30
minutes from the initiation of polymerization, methanol was added
to terminate polymerization reaction. After the pressure was
released, the polymer solution was withdrawn, and the polymer
solution was washed by using an "aqueous solution obtained by
adding 5 ml of concentrated hydrochloric acid based on 1 liter of
water" in a ratio of 1:1 (aqueous solution:polymer solution) to
transfer the catalyst residue into the aqueous phase. After this
catalyst mixed solution was allowed to stand still, the aqueous
phase was separated and removed, and the remainder was further
washed with distilled water twice to subject the polymerization
liquid phase to oil-water separation. The polymerization liquid
phase having been subjected to oil-water separation was contacted
with acetone in an amount of 3 times as much as the polymerization
liquid phase with vigorous stirring, to precipitate a polymer.
Then, the polymer was sufficiently washed with acetone, and the
solid part (copolymer) was collected by filtration. The solid part
was dried at 130.degree. C. and 350 mmHg for 12 hours in a stream
of nitrogen.
[0147] The propylene/ethylene copolymer obtained as above had an
intrinsic viscosity [.eta.], as measured in decalin at 135.degree.
C., of 2.4 dl/g, a SP value of 0.94, a glass transition temperature
of -28.degree. C., an ethylene content of 24% by mol, and a
molecular weight distribution (Mw/Mn), as measured by GPC, of
2.9.
Example 1
[0148] 70 Parts by weight of the syndiotactic
propylene/butene/ethylene random copolymer (A-1) obtained in
Polymerization Example 1, 20 parts by weight of isotactic
polypropylene (B-1) (homopolymer, MFR (230.degree. C., load of 2.16
kg, the same measuring conditions shall apply hereinafter): 0.5
g/10 min), 10 parts by weight of a 1-butene homopolymer (C-1) (MFR:
2.0 g/10 min), 2 parts by weight of a carbon black masterbatch (for
coloring the resulting composition black, the same shall apply
hereinafter) and 2 parts by weight of a silicone oil (available
from Dow Corning Toray Silicon Co., Ltd., trade name: SH100 (100
cs)) were stirred and mixed by a batch type high-speed mixer and
then kneaded by a twin-screw extruder whose highest temperature had
been set at 230.degree. C., to obtain pellets of a composition
(I).
[0149] The resulting pellets of the composition (I) were extruded
by a sheet extrusion molding machine equipped with a T-die having
been set at a die temperature of 210.degree. C., and passed between
an embossing roll (roll temperature: 90.degree. C.) placed just
behind the die and a pinch roll to obtain an embossed sheet. The
thickness of the embossed sheet was 0.5 mm, and the maximum depth
of the embossed pattern was 180 .mu.m. This embossed sheet was
subjected to positive vacuum forming using an instrument panel mold
under the conditions of a sample temperature of 145.degree. C. The
resulting form had no problem with its appearance and had good
appearance.
Using a Japan Society for the Promotion of Science-type abrasion
tester (manufactured by Toyo Seiki Seisaku-Sho, Ltd.), a test
specimen of 2 mm thickness obtained from the sheet having been
subjected to no vacuum forming was abraded with a 45R abrasion
indenter of 470 g made of SUS, whose tip had been covered with a
cotton canvas of #10, under the conditions of 23.degree. C., a
number of reciprocating abrasion times of 100, a reciprocating
abrasion rate of 33 times/min and a stroke of 100 mm, and a change
in gloss after the abrasion was determined in the following
manner.
Change in gloss=gloss before abrasion-gloss after abrasion
[0150] The change in gloss under the above conditions was 4%.
[0151] Further, from the pellets of the composition (I), a grip was
produced under the same injection molding conditions as above. On
the resulting grip, a cotton canvas having a width of 3 cm was
hung, and the grip was subjected to an abrasion test of 300
reciprocating abrasion times under a load of 300 g, as shown in the
FIGURE. A change after the test was visually observed and evaluated
by the following criteria.
[0152] 5 points: No scratch was observed.
[0153] 4 points: A scratch was slightly observed.
[0154] 3 points: A scratch was apparently observed.
[0155] 2 points: The surface was scraped and abraded.
[0156] 1 point: The surface was markedly abraded.
[0157] The above grip scored 5 points.
[0158] Furthermore, the embossed sheet was placed in a Geer oven at
110.degree. C. for 24 hours and taken out, then the gloss of the
sheet was compared with the gloss value measured before the sheet
was placed in the Geer oven, and a change in gloss due to heat
aging was determined in the following manner.
Change in gloss=gloss before heat treatment-gloss after heat
treatment
[0159] The change in gloss was 2%.
Example 2
[0160] In a Henschel mixer, 40 parts by weight of isotactic
polypropylene (homopolymer, MFR: 12 g/10 min), 60 parts by weight
of pellets of an oil-extended product of an
ethylene/propylene/5-ethylidene-2-norbornene copolymer rubber (EPDM
(D-1), oil extension quantity: 40 parts by weight, oil: mineral
oil-based paraffin oil, Mooney viscosity ML1+4 (100.degree. C.):
80, ethylene content: 79% by mol, iodine value: 11), 0.2 part by
weight of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane as a
crosslinking agent (POX) and 0.3 part by weight of divinylbenzene
(DVB) as a crosslinking assistant were sufficiently stirred and
mixed, and the mixture was fed to a twin-screw extruder set at
160.degree. C. to 220.degree. C. and subjected to dynamic
crosslinking to prepare pellets of a crosslinked thermoplastic
elastomer (TPV-1). From 40 parts by weight of the pellets of this
TPV-1, 30 parts by weight of the syndiotactic
propylene/butene/ethylene random copolymer (A-1) obtained in
Polymerization Example 1, 20 parts by weight of an isotactic
propylene/ethylene random copolymer (B-2) (MFR: 10 g/10 min,
ethylene content: 2.5% by mol), 10 parts by weight of a 1-butene
homopolymer (C-1), 2 parts by weight of a carbon black masterbatch
and 2 parts by weight of a silicone oil (the same as that in
Example 1), pellets of a composition (II) were obtained in the same
manner as in Example 1.
[0161] From the resulting pellets of the composition (II), an
embossed square plate was produced by the use of an injection
molding machine (M-150 manufactured by Meiki Co., Ltd., cylinder
preset temperature: 220.degree. C.). Moldability and appearance of
the embossed square plate were good. Before and after the abrasion
test of the Japan Society for the Promotion of Science, gloss was
measured in the same manner as in Example 1. The change in gloss
was 7%.
[0162] Further, from the pellets of the composition (II), a grip
was produced under the same injection molding conditions as in
Example 1, and the grip was subjected to a reciprocating abrasion
test. A change after the test was evaluated in the same manner as
in Example 1.
[0163] The above grip scored 4 points.
[0164] Furthermore, the embossed square plate was placed in a Geer
oven at 110.degree. C. for 24 hours similarly to Example 1, and a
change in gloss due to heat aging was determined.
[0165] The change in gloss was 1%.
Example 3
[0166] From 70 parts by weight of the syndiotactic
propylene/ethylene random copolymer (A-2) obtained in
Polymerization Example 2, 20 parts by weight of isotactic
polypropylene (B-1), 10 parts by weight of a 1-butene homopolymer
(C-1), 2 parts by weight of a carbon black masterbatch and 2 parts
by weight of a silicone oil (the same as that in Example 1),
pellets of a composition (III) were obtained in the same manner as
in Example 1.
[0167] From the resulting pellets of the composition (III), an
embossed-sheet was produced in the same manner as in Example 1, and
the embossed sheet was subjected to positive vacuum forming. The
resulting form had no problem with its appearance and had good
appearance.
[0168] Using the sheet having been subjected to no vacuum forming,
an abrasion test of the Japan Society for the Promotion of Science
was carried out in the same manner as in Example 1, and a change in
gloss after the test was determined.
[0169] The change in gloss under the above conditions was 5%.
[0170] Further, from the pellets of the composition (III), a grip
was produced under the same injection molding conditions as in
Example 1, and the grip was subjected to a reciprocating abrasion
test. A change after the test was evaluated in the same manner as
in Example 1.
[0171] The above grip scored 5 points.
[0172] Furthermore, a change in gloss due to heat aging was
determined in the same manner as in Example 1.
[0173] The change in gloss was 2%.
Example 4
[0174] To 40 parts by weight of the syndiotactic propylene/ethylene
random copolymer (A-2) obtained in Polymerization Example 2, 20
parts by weight of isotactic polypropylene (B-1), 10 parts by
weight of a 1-butene homopolymer (C-1), 30 parts by weight of EPDM
(D-1), 2 parts by weight of a carbon black masterbatch and 2 parts
by weight of a silicone oil (the same as that in Example 1) were
added 0.2 part by weight of
2,5-dimethyl-2,5-di(tert-butylperoxy)hexane (POX-1) as a
crosslinking agent and 0.2 part by weight of divinylbenzene (DVB)
as a crosslinking assistant, and they were sufficiently stirred and
mixed in a Henschel mixer. The mixture was fed to a twin-screw
extruder set at 160.degree. C. to 220.degree. C. and subjected to
dynamic crosslinking to obtain pellets of a composition (IV).
[0175] From the resulting composition (IV), an embossed sheet was
produced in the same manner as in Example 1, and the embossed sheet
was subjected to positive vacuum forming. The resulting form had no
problem with its appearance and had good appearance.
[0176] Using the sheet having been subjected to no vacuum forming,
an abrasion test of the Japan Society for the Promotion of Science
was carried out in the same manner as in Example 1, and a change in
gloss after the test was determined.
[0177] The change in gloss under the above conditions was 7%.
[0178] Further, a change in gloss due to heat aging was determined
in the same manner as in Example 1.
[0179] The change in gloss was 2%.
Example 5
[0180] From 40 parts by weight of the pellets of TPV-1 obtained in
Example 2, 30 parts by weight of the syndiotactic
propylene/butene/ethylene random copolymer (A-1), 10 parts by
weight of an isotactic propylene/ethylene random copolymer (B-2)
(MFR: 10 g/10 min, ethylene content: 2.5% by mol), 10 parts by
weight of a syndiotactic syndiotactic homopolymer (B-3) (MFR: 1
g/10 min), 10 parts by weight of a 1-butene homopolymer (C-1), 2
parts by weight of a carbon black masterbatch and 2 parts by weight
of a silicone oil (the same as that in Example 1), pellets of a
composition (V) were obtained in the same manner as in Example
1.
[0181] From the resulting pellets of the composition (V), an
embossed sheet was produced in the same manner as in Example 1, and
the embossed sheet was subjected to positive vacuum forming. The
resulting form had no problem with its appearance and had good
appearance.
[0182] Using the sheet having been subjected to no vacuum forming,
an abrasion test of the Japan Society for the Promotion of Science
was carried out in the same manner as in Example 1, and a change in
gloss after the test was determined.
[0183] The change in gloss under the above conditions was 6%.
[0184] Further, a change in gloss due to heat aging was determined
in the same manner as in Example 1.
[0185] The change in gloss was 1%.
[0186] Furthermore, from the pellets of the composition (VI), a
grip was produced under the same injection molding conditions as in
Example 1, and the grip was subjected to a reciprocating abrasion
test. A change after the test was evaluated in the same manner as
in Example 1.
[0187] The above grip scored 4 points.
Comparative Example 1
[0188] From 70 parts by weight of the syndiotactic
propylene/ethylene random copolymer (A-1) obtained in
Polymerization Example 1, 30 parts by weight of isotactic
polypropylene (B-1), 2 parts by weight of a carbon black
masterbatch and 2 parts by weight of a silicone oil (the same as
that in Example 1), pellets of a composition (VI) were obtained in
the same manner as in Example 1.
[0189] From the resulting composition (VI), an embossed sheet was
produced in the same manner as in Example 1, and the embossed sheet
was subjected to positive vacuum forming. The resulting form had no
problem with its appearance and had good appearance.
[0190] Using the sheet having been subjected to no vacuum forming,
an abrasion test of the Japan Society for the Promotion of Science
was carried out in the same manner as in Example 1, and a change in
gloss after the test was determined.
[0191] The change in gloss under the above conditions was 5%.
[0192] Further, from the pellets of the composition (VI), a grip
was produced under the same injection molding conditions as in
Example 1, and the grip was subjected to a reciprocating abrasion
test. A change after the test was evaluated in the same manner as
in Example 1.
[0193] The above grip scored 4 points.
[0194] Furthermore, a change in gloss due to heat aging was
determined in the same manner as in Example 1.
[0195] The change in gloss was 7%.
Comparative Example 2
[0196] From 40 parts by weight of the pellets of the crosslinked
thermoplastic elastomer (TPV-1) used in Example 2, 30 parts by
weight of the syndiotactic propylene/butene/ethylene random
copolymer (A-1), 30 parts by weight of an isotactic
propylene/ethylene random copolymer (B-2), 2 parts by weight of a
carbon black masterbatch and 2 parts by weight of a silicone oil
(the same as that in Example 1), pellets of a composition (VII)
were obtained in the same manner as in Example 1.
[0197] From the resulting pellets of the composition (VII), an
embossed square plate was produced by the use of an injection
molding machine similarly to Example 2. Moldability and appearance
of the embossed square plate were good. Before and after the
abrasion test of the Japan Society for the Promotion of Science,
gloss was measured in the same manner as in Example 1. The change
in gloss was 8%.
[0198] Further, from the pellets of the composition (VII), a grip
was produced under the same injection molding conditions as in
Example 1, and the grip was subjected to a reciprocating abrasion
test. A change after the test was evaluated in the same manner as
in Example 1.
[0199] The above grip scored 4 points. Furthermore, the embossed
square plate was placed in a Geer oven at 110.degree. C. for 24
hours similarly to Example 2, and a change in gloss due to heat
aging was determined. The change in gloss was 9%.
Comparative Example 3
[0200] From 70 parts by weight of an existing
propylene/butene/ethylene copolymer having an isotactic structure
(intrinsic viscosity [.eta.] as measured in decalin at 135.degree.
C.: 2.5 dl/g, propylene content: 62% by mol, ethylene content: 10%
by mol, 1-butene content: 28% by mol, molecular weight distribution
(Mw/Mn) as measured by GPC: 2.2), 20 parts by weight of isotactic
polypropylene (B-1), 10 parts by weight of a 1-butene homopolymer
(C-1), 2 parts by weight of a carbon black masterbatch and 2 parts
by weight of a silicone oil (the same as that in Example 1),
pellets of a composition (VIII) were obtained in the same manner as
in Example 1.
[0201] From the resulting composition (VIII), an embossed sheet was
produced in the same manner as in Example 1, and the embossed sheet
was subjected to positive vacuum forming. As for the appearance of
the resulting form, embossed patterns almost eliminated were found
here and there, and the appearance was bad.
[0202] Using the sheet having been subjected to no vacuum forming,
an abrasion test of the Japan Society for the Promotion of Science
was carried out in the same manner as in Example 1, and a change in
gloss after the test was determined.
[0203] The change in gloss under the above conditions was 58%.
[0204] Further, from the pellets of the composition (VIII), a grip
was produced under the same injection molding conditions as in
Example 1, and the grip was subjected to a reciprocating abrasion
test. A change after the test was evaluated in the same manner as
in Example 1.
[0205] The above grip scored 3 points.
[0206] Furthermore, a change in gloss due to heat aging was
determined in the same manner as in Example 1.
[0207] The change in gloss was 2%.
[0208] The results of Examples 1 to 5 and Comparative Example 1 to
3 are set forth in Table 1.
TABLE-US-00001 TABLE 1 Comp. Comp. Comp. Ex. 1 Ex. 2 Ex. 3 Ex. 4
Ex. 5 Ex. 1 Ex. 2 Ex. 3 Syndiotactic 70 30 30 70 30
propylene/butene/ethylene random copolymer (A-1) Syndiotactic 70 40
propylene/ethylene random copolymer (A-2) Isotactic 70
propylene/butene/ethylene random copolymer (A-3) Isotactic
propylene 20 20 20 10 30 20 homopolymer (B-1) Isotactic 20 30
propylene/ethylene random copolymer (B-2) Syndiotactic propylene 10
homopolymer (B-3) 1-Butene homopolymer (C-1) 10 10 10 10 10 10 EPDM
(D-1) 30 TPV-1 40 40 40 Carbon black masterbatch 2 2 2 2 2 2 2 2
Silicone oil 2 2 2 2 2 2 2 2 POX-1 0.2 DVB 0.2 Sheet extrusion
moldability AA -- AA AA AA AA -- AA (T-die extrusion) Vacuum
formability AA -- AA AA AA AA -- BB Injection moldability AA -- --
-- AA -- Abrasion test of the Japan 4 7 5 7 6 5 8 58 Society for
the Promotion of Science, Change in gloss (%) Abrasion test by
cotton canvas 5 4 5 -- 4 4 4 3 (point (s)) Heat aging resistance,
Change 2 1 2 2 1 7 9 2 in gloss (%) AA: good, BB: bad
INDUSTRIAL APPLICABILITY
[0209] According to the present invention, a polyolefin composition
excellent in scratch resistance, abrasion resistance, heat aging
resistance and processability into parts can be proposed.
* * * * *